Algicidal agents

ABSTRACT

Algicidal compositions of, and methods of combating algae including slime bacteria, using certain N-chlorophenyl-alkylene polyamines and their corresponding water soluble salts, some of which are known, which possess algicidal and slime bactericidal properties and which may be produced by conventional methods.

United States Patent Daum et al. Feb. 29, 1972 [54] ALGICIDAL AGENTS 56]V I I Reterences V I p 721 Inventors: Werner Daum, Krefeld-Bockum;wilh'ied UNITED STATES PATENTS Paul; Pauli, both of Krefeld, all of2,829,164 4/1958 Rocklin ..260/570.5 Germany 3,125,486 3/ 1964 Schmitzet a1. ..71/67 Assigneez Farbeniabriken Bayer 3, 1 1 5 l Wehner ....7 lLeverkusen, Germany 3,247,053 4/1966 Hodge ...71/67 3 .7 3,394,1377/1968 Morris 71/67 X [22] Filed: [)ecfll, 1968 3,466,162 9/1969 Glooret a1 ..71/67 [21] APPI'NO: 783l34 Primary Examiner.1ames 0. Thomas, Jr.

Attorney-Burgess, Dinklage & Sprung [30] Foreign Application PriorityData [57] ABSTRACT Dec. 27, 1967 Germany ..P 16 43 384.4

Algicidal compositions of, and methods of combating algae in- 52 us. CL..71/67 eluding Slime bacteria, Sing main [51] Int Cl A01 9/00 Aoln23/00 polyamines and their corresponding water soluble salts, some [58]Field of's'earchm of which are known, which possess algicidal and slimebactericidal properties and which may be produced by conventionalmethods.

7 1 9 51 1 N Drawings ALGICIDAL AGENTS The present invention relates toand has for its objects the provision for algicidal compositions ofN-chlorophenyl-alkylene polyamines and their corresponding water solublesalts, some of which are known, and which possess algicidal, includingslime bactericidal, properties, in the form of mixtures of suchcompounds with solid dispersible carrier vehicles and/or with liquiddispersible carrier vehicles containing a surface-active agent, andmethods for using such compounds in a new way especially for combatingalgae and slime bacteria, with other and further objects becomingapparent from a study of the within specification and accompanyingexamples.

It has been found in accordance with the present invention that certainN-chlorophenyl-alkylene polyamines, some of which are known, of theformula lower alkyl substituted formamidino, imidazoline ortetrahydropyrimidine with the proviso that R and R when taken togetherwith the adjacent N-atom form piperrazino, and Z is a phenyl radical ofthe formula in which X is hydrogen, chloro or lower alkyl, and 5,

n is a whole number from 2 to 5,

at least two of the substituents X being chlorine; and the correspondingwater-soluble salts thereof, exhibit strong algicidal, including slimebactericidal, properties.

It is very surprising that such N-chlorophenyl-alkylene polyamines andtheir corresponding water-soluble salts which are usable according tothe present invention have a considerably effective algicidal activityand slime bactericidal activity while concomitantly having a much lowertoxicity than other algicides known from the prior art, such as sodiumpentachlorophenolate and organic mercury compounds. The algicidalcompositions and methods of combating algae and/or slime bacteria usingsuch active compounds according to the present invention thereforerepresent a valuable enrichment of the art.

The preferred compounds are those in which, in formula (la), Z is aphenyl radical per-substituted in the above sense, the group (NH-A),contains up to three nitrogen atoms and up to six carbon atoms, and R ishydrogen and R is hydrogen, or imidazoline or R and R together with theadjacent nitrogen atom is a piperazine ring system: and thecorresponding water soluble salts thereof.

The present invention also provides certain new N chlorophenyl-alkylenepolyamines of formula (la) and their corresponding water soluble salts,i.e., those preferred compounds in which 2 is a dior tri-chlorinatedphenyl radical, and the group (NHA),,, as well as R and R possess theimmediately aforesaid meaning, are new.

The instant new compounds may be prepared in the same manner as theknown compounds, i.e., by known methods, as may be seen for example fromUS. Pat. No. 2,829,164 or German Auslegeschrift No. 1,136,060.

The method is illustrated by the following typical example:

Advantageously, in accordance with the present invention, in the variousformulas herein:

m is a whole number from 1-4, especially 1-3; A represents alkylenehaving 2-!0 carbon atoms, including straight and branched chains such asdi-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nonaand deca-methylene,especially C or C or C alkylene; more especially ethylene (Cl-l,-CHpropylene-1,3 (CH CH CH propylene l,2 (CH CH[CH,,]); butylene- -l,4,-l,3 and -l,2; pentylene- -1,5, -l,4 -l,3 and -l,2; hexylene- -l,6,-l,5,-l,4, -l,3, -l,2; 2,2- dimethyl-butylenel ,4;l,2,3-tri-methyl-propylenel ,3; and the like; and particularlydimethylene or ethylenel ,2; methyl-dimethylene or propylenel ,2;tetramethylene or butylene-l,4 and hexamethylene or hexylene- 1 ,6; Rrepresents hydrogen; R represents hydrogen; CHO, i.e., formyl; CONHi.e., aminocarbonyl; lower alkanoyl, especially C alkanoyl such asacetyl,

propionyl, butyryl, and the like, i.e., C or C alkylcarbonyl or C or C,.alkyl-CO; such lower alkanoyl, as defined above, which is substitutedwith a chloro, carboxyl or alkali metal salt of carboxyl, includingchloro lower alkanoyl, especially chloro-substituted C alkanoyl such aschloro acetyl; aand fl-chloro propionyl; a-, B- and 'y-chloro butyryl;and the like; i.e., chloro-substituted C or C, -alkyl-carbonyl; and moreespecially chloro acetyl; carboxyl (i.e., COOH) lower alkanoyl,especially carboxyl-substituted C alkanoyl such as carboxyl acetyl ormalon-mono-yl (HOOC-CH -CO-), B-carboxylpropionyl or succin-mono-yl(HOOCCH -CH CO); 'y-carboxyl-butyryl or glutar-mono-yl (HOOC-CH CH CH-CO-); and the like; i.e., carboxyl-substituted C.. or C,,-alkylcarbonyl; and more especially B-carboxyl-propionyl; and alkalimetal salt of carboxyl (i.e.,-COO-alkali metal) lower alkanoyl,especially alkali metal (e.g., Na, K, Li, and the like) salt ofcarboxyl-substituted C alkanoyl such as the monosodium and monopotassiumsalts of carboxyl acetyl or malon-mono-yl (Na-and K- OOC-CH -CO); themonosodium and monopotassium salts of 'y-carboxyl-butyryl orglutarmono-yl (Na-'- and K- OOCCH,CH,CH CO and the like; i.e., monalkalimetal salts of carboxylsubstituted C or C alkyl carbonyl; and moreespecially monosodium succinate-mono-yl;

NH & tonnamidlno, Le. C

N Hg

lower alkyl substituted formamidino, such as methyl, ethyl, nandiso-propyl, n-, iso-, secand tert.-butyl substituted formamidino andwhen two alkyl groups taken together with the N-atoms of the formamidinogroup form an imidazolino or tetrahydro-pyrimidino nucleus, moreespecially an imidazolino nucleus, i.e.,

with the proviso that R and R when taken together with the adjacentnitrogen atom form piperazino (i.e., in the latter case R and R togetherforming the 3-aza-l,5- pentylene bridge); Z represents an at leastdichloro-substituted phenyl radical of the formula in which X representshydrogen; chloro; and/or lower alkyl such as methyl, ethyl, nandiso-propyl, n-,

iso-, sec.- and tert.-butyl, and the like, especially C or C or C alkyl,and particularly methyl; and

n is a whole number from 2-5 such that at least two of the substituentsX are chloro;

2 including in particular all di-, triand tetra-chlorophenyl as well aspentachlorophenyl; all dichloro-mono to tri methyl, ethyl, nandiso-propyl, n-, iso-, sec.- and ten.- butyl, and the like, -phenyl; alltrichloro-mono to dimethyl, ethyl, nand iso-propyl, n-, iso-, sec.- andten.- butyl, and the like, -phenyl; all tetrachloro-mono -methyl, ethyl,nand iso-propyl, n-, iso-, sec.- and tert.-butyl, and the like, -phenyl;and especially di, tri, tetra and penta chlorophenyl, and di totetra-chloro- -mono to tri C or C or C, or C -alkyl- -pheny1;

Besides of water-soluble metal salts of carboxyl C -C alkanoylsubstituted compounds such compounds also contemplating thecorresponding water-soluble ammonium salts thereof, e.g., with hydrogenhalides (HCl, HBr, HF and H1); sulfuric acids including lower alkyl,especially C alkyl, substituted sulfuric acids; lower alkanoic acidsincluding acetic, propionic, butyric, and the like, acids, especially Calkanoic acids; benzoic and salicylic acids, and the like; i.e., thecorresponding hydrochlorides, hydrobromides, hydrofluorides,hydroiodides, hydrogen sulfates, lower alkyl-sulfates, lower alkanoates,e.g., acetates, propionates, butyrates, and benzoates, salicylates,etc., and the like, all of which are water soluble.

Preferably, the N-chlorophenyl-alkylene polyamines have the formula inwhich m is a whole number from 1-3; R and R are hydrogen or R representshydrogen and R represents formamidino, lower alkyl formamindino and whentwo alkyl groups taken together with the N-atoms of the formamidinogroup form an imidazolino or a tetrahydro-pyrimidino nucleus and withthe proviso that R and R when taken together with the adjacent N-atomform a piperazino nucleus. X is hydrogen, chloro and/or lower alkyl; andn is a whole number from 2-5, at least two of the substituents X beingchloro.

As aforesaid, the new compounds are those in which m is 1-3, the group(Nl-l--A),, contains 1-3 N-atoms and 2-6 carbon atoms, R and R arehydrogen or together form a piperazino group and Z is dichloro-phenyland trichlorophen- Suitable amines are for example: ethylenediamine,propylene-1,3-diamine, propylene-1,2- diamine, tetramethylenediamine,hexamethylenediamine,

diethylenetriamine, triethylenetetramine, tetraethylenepentamine,dipropylene- 1 ,2-triamine, dihexylenel ,6-triamine andB-aminoethyl-piperazine.

In general, at least 2 mols, preferably approximately 10 to about 20mols, of amine is used per mol of halogen compound. If desired, thereaction may be carried out in the presence of a high-boiling, inertorganic solvent, for example diphenyl ether. Preferably, however, excessamine is used as solvent. The reaction is, in general, carried out inthe temperature range of about 50 to 250 C. When a halogen compound witharomatically attached halogen is used, the work is carried outespecially at higher temperatures up to 250 C. In the case of thehexaand penta-halogenobenzenes, the temperature range of 1 10 to C. ispreferred, but in the case of the tetraand tri-halogenobenzenes thetemperature range of to 220 C. is preferred. The working up of themixtures takes place in known manner, the halogen hydride liberated inthe reaction being preferably bound (before removal of the whole of theexcess amine) by addition of an inorganic base, preferably in aqueousform (for example NaOH, KOH, Ca (03):, Na CO and the like). Afterremoval of the excess amine, the amino compound formed is isolated,optionally after further reaction with an acid anhydride or acid halideof a lower aliphatic carboxylic acid or urea or s-lower alkyl thioureasalts or with formic acid.

As noted above, the N-chlorophenyl-alkylene polyarnines of formula (1a)and their corresponding salts usable according to the present inventionare distinguished from other known algicides by their particularly lowtoxicity. The use of the instant compounds, therefore, presents-nodifficulties, in contrast to customary agents such as sodiumpentachlorophenolate or organic mercury compounds which are highlytoxic.

The algicidal agents of the present invention are suitable for thecontrol of the most diverse algae, for example for the control ofChlorophycae, Phaeophyceae, Cyanophyceae, Diatomeae, and the like. Theamounts required can be readily ascertained by preliminary experiments;in general, concentrations of 1-15 mg./l. of algae-containing waterprove sufficient.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert pesticidal diluents or extenders, i.e., conventionalpesticidal dispersible carrier vehicles, such as solutions, emulsions,suspensions, emulsifiable concentrates, spray powders, pastes, solublepowders, dusting agents, granules, etc. These are prepared in knownmanner, for instance by extending the active compounds with conventionalpesticidal inert dispersible liquid diluent carriers and/or inertdispersible solid carriers optionally with the use of carrier vehicleassistants, e.g., conventional pesticidal surface-active agents,including emulsifying agents and/or dispersing agents, whereby, forexample, in the case where water is used as diluent, organic solventsmay be added as auxiliary solvents. The following may be chieflyconsidered for use as conventional carrier vehicles for this purpose:dispersible liquid diluent carriers, including inert organic solvents,such as aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.),halogenated, especially chlorinated, aromatic hydrocarbons (e.g.,chlorobenzenes), parafiins (e.g., petroleum fractions), chlorinatedaliphatic hydrocarbons (e.g., methylene chloride etc.), alcohols (e.g.,methanol,

ethanol, propanol, butanol, etc.), amines (e.g., ethanolamine, etc.),ethers, ether-alcohols (e.g., glycol monomethyl ether, etc.), amides(e.g., dimethyl formamide, etc.), sulfoxides (e.g., dimethyl sulfoxide,etc.), ketones (e.g., acetone, etc.), and/or water; as well asdispersible finely divided solid carriers, such as ground naturalminerals (e.g., kaolins, alumina, silica, chalk, i.e., calciumcarbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g.,highly dispersed silicic acid, silicates, e.g., alkali silicates, etc.);whereas the following may be chiefly considered for use as conventionalcarrier vehicle assistants, e.g., surface-active agents, for thispurpose: emulsifying agents, such as nonionic and/or anionic emulsifyingagents (for instance, polyethylene oxide esters of fatty acids,polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, arylsulfonates, etc., and especially alkyl aryl-polyglycol ethers, magnesiumstearate, sodium oleate, etc.); and/or dispersing agents, such aslignin, sulfite waste liquors, methyl cellulose, etc.

As will be appreciated by the artisan, the active compounds according tothe instant invention may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other algicides fungicides,herbicides, insecticides, acaricides, bactericides, etc., if desired, orin the form of particular dosage preparations for specific applicationmade therefrom, such as solutions, emulsions, suspensions, powders,pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95 percent, andpreferably 0.5-90 percent, by weight of mixture, whereas carriercomposition mixtures suitable for direct applications or fieldapplication (e.g., water) generally contemplate those in which theactive compound is present in an amount substantially between about0.000l2.5 percent, by weight of the mixture. Thus, the present inventioncontemplates overall algicidal compositions which comprise mixtures of aconventional dispersible carrier vehicle such as (1) a dispersiblecarrier solid, and/or (2) a dispersible carrier liquid such as an inertorganic solvent and/or water preferably including a surface-activeeffective amount of a carrier vehicle assistant, e.g., a surface-activeagent, such as an emulsifying agent and/or a dispersing agent, and anamount of the active compound which is effective for the purpose inquestion and which is generally between about 0.0001-95 percent byweight of the mixture.

Furthermore, the present invention contemplates methods of selectivelykilling, controlling or combating algae or slime bacteria, whichcomprise applying to at least one of (a) such algae, (b) such slimebacteria or (c) the corresponding habitat, i.e., the locus to beprotected (which is normally water), an algicidally or slimebactericidally effective or toxic amount of the particular activecompound of the invention alone or together with a carrier vehicle asnoted above. The instant formulations or compositions are applied in theusual manner, for instance by spraying, atomizing, vaporizing,scattering, dusting, watering, sprinkling, pouring, and the like.

Preferably, compounds used as algicides or slime bactericides inaccordance with the invention are used as such, or if desired, in theform of their water-soluble ammonium salts, such as the correspondinghydrochlorides, sulfates, acetates, benzoates, salicylates, and thelike, or in the case of carboxyl, alkanoyl substituted compounds theyare used as their watersoluble alkali salts. Solutions of thesecompounds in particular in a lower alcohol, glycol or glycol ether can,of course, also be used. in the case of compounds which still have afree carboxyl group, alkali metal hydroxides (e.g., sodium, potassium)are preferred for the preparation of their water-soluble salts, i.e., inthe conventional manner.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases, it ispossible to go above or below the aforementioned concentration ranges.

The outstanding algicidal effectiveness of particularhalophenyl-alkyleneamines within the scope of the present invention isillustrated, without limitation, by the following example:

EXAMPLE 1 The inhibition values, for the algicidal effectiveness of theparticular active compounds tested, were determined in the followingmanner:

A common mixed culture of green algae, brown algae, blue algae anddiatoms was grown for 2 weeks in neutral nutrient solutions (Allen'snutrient solutions), containing, per liter of water, 1,000 mg. sodiumnitrite, 513 mg. Epsom salts, 250 mg. dipotassium hydrogen phosphate, 50mg. ammonium chloride, 50 mg. calcium chloride and 3 mg. iron(SD-chloride. After the algae had been allowed to grow undisturbed forthis period, various amounts of the algicidal compounds of the inventionwere added correspondingly to the then deep-green colored nutrientsolutions.

Algicidally effective substances decolorize such nutrient solutions. Theinhibition values stated in Table 1 below are the minimum amounts, inmg./l. (or p.p.m., as the case may be), at which the nutrient solutionswere still completely colorless even after 6 weeks cultivation, i.e.,when treated with the instant active compounds:

(1 0 N '4 fid s lerep ien b eth saett a une (19,)N'-(2,4,S-trichloro-phenyl)-tri(propylene-l',2)-

tetramine 20 (20,) N-[p(2,4,$- trichlorophenyl-amino)- ethyll-piperazint(2l,) N-[B-(2,5-dichloro-phenyl-amino)-ethyl]- piperazine 2 (22,)N-lB-(2,4,6-trichloro-3,S-dimethyl-phenylamino)-ethyl] piperazine (23,)N-(2,4,6-trichloro-3,S-dimethyl-phenyl)- hexamethylendiamine l (25,)N-(2,4,5-trichloro-phenyl)-hexamethylancdiamine hydrochloride 5 (26,)N-(2,4,5-trichloro-phenyl)-tri-ethylene diamine The same inhibitionvalues as given in Table l are achieved with equivalent amounts of thecorresponding ammonium salts (e.g., salts with hydrohalogen acids suchas the corresponding ammonium chlorides, bromides, fluorides andiodides, and with lower aliphatic carboxylic acids such as thecorresponding ammonium formates, acetates, propionates, butyrates,etc.).

The practical effectiveness of the compounds of formula (Ia) above canalso be seen from the following example:

EXAMPLE 2 in a newly installed industrial closed cooling system(capacity: 3.5 cubic meters of water), the glass condensers and pipeswhich were accessible to daylight always showed strong growth of algaeafter a few weeks, so that the cooling effect was appreciably impaired.Without draining off the water, there were then added to the coolingsystem 100 ml. of a 35 percent solution ofN-(pentachlorophenyl)-hexamethylenediamine acetate (24,) in methanol.After about 8 days the algae were dead. The circulation systemfunctioned and cooling was effected without trouble in the time whichfollowed; even after 6 months operation, living algae could not beisolated from the water of the circulation system. Analogous results areobtainable with the other compounds of formula (In) above according tothe invention.

EXAMPLE 3 As aforesaid, the compounds of the formula (la) above in whichZ is a dior tri-chlorinated phenyl radical, and the group -(NHA),,,contains up to three nitrogen atoms and up to six carbon atoms, and inwhich R and R are hydrogen, or R or R together with the nitrogen atomform a piperazine ring system, or their water-soluble salts, are new.

These preferred compounds in particular are also very suitable for thecontrol of slime bacteria. Such preferred compounds have proved, forexample, outstandingly effective against slime organisms which wereisolated from a pulp-conveying channel of a paper factory. Thebactericidal effect was tested as follows:

To corresponding Allen's nutrient solutions was added 1 percentcaprolactam as a carbon source and an additional nitrogen source for theslime organisms and, after sterilization, a particular active compoundof the preferred group of com pounds, for exampleN-(pentachlorophenyl)-hexamethylenediamine as well asZ-[m-(pentachlorophenylamino)-hexylamino]-imidazoline-1 methosulfate (16in amounts of 05-50 mg./l. The nutrient solutions were then infectedwith a mixed culture of the above-mentioned slime organisms. Thenutrient solutions remained completely clear during a three-week cultureperiod, even after reinfection several times, that is the slimeformation visible after 3-4 days in nutrient solutions free from theactive compound, did not occur in a 3-week period where the particularactive compound was present.

The invention is also illustrated, without limitation, by the followingfurther examples.

EXAMPLE 4 41.2 g. 1,2,4-trichloro-benzene (0.23 mol) and 254 g.hexamethylenediamine (2.2 mols) are heated to 200 C. for 23 hours. Thebulk of the excess hexamethylenediamine is distilled off in a water-jetvacuum, the remaining residue is treated with a mixture of toluene andabout 20 g. of sodium hydroxide in water, the toluene phase is washedout with water and, before distillation, drying may be carried out withsodium hydroxide or potassium carbonate. Yield: 52.5 g. of N-(2,5-dichloro-phenyl)-hexamethylenediamine of the formula m g t mm. Hg.;Calculated: N 10.72%

I- 'ound: l0.5-l0.7%

In the same manner, there are obtained:

From 1,2,4-trichloro-benzene and N-(fi-amino-ethyD- piperazine, thecompound N-[/3-(2,5-dichloro-phenyl-amino ethyll-piperazine of theformula Calculated:

Found:

From 1,2,4-trichloro-benzene and technical-gradedi(propylene-1,2)-triamine, the compoundN'-(2,5-dichlorophenyl)-di(propylene-l ',2')triamine of the formuladiethylenetriamine, the compound N'-(2,5-dichloro-phenyl)-diethylenetriamine of the formula bl -138 c./0.0s mm. Hg;

Calculated: N 16.93% Cl 28.55% Found: 16.0% 27.6%

EXAMPLE 5 431.8 g. 1,2,4,S-tetrachloro-benzene (2 mols) and 2,320 g.hexamethylenediamine (20 mols) are kept at 200 C. for 7 hours and thenworked up as described in Example 4 above.

Yield: 496 g. of N-(2,4,5-trichloro-phenyl)-hex+ amethylenediamine ofthe formula l O1--NH-CeHm-NH2 b.p. 153 C./0.06 mm. Hg;

Hydrochloride (from ethylene chloride) m.p. 124 C., i.e.,N-(2,4,5-trichloro-phenyl)-hexamethylenediamine hydrochloride (25,)

Calculated: Found:

In the same manner, there are obtained:

From l,2,4,5-tetrachloro-benzene and N-(fi-amino-ethyD- piperazine, thecompound N-[/3-(2,4,5-trichloro-phenyl)- amino)-ethyl]-piperazine of theformula Calculated: N 13.63% Found: l3.4%

From l,2,4,5-tetrachloro-benzene and technical-grade diethylenetriamine,the compound N-(2,4,5-trichloro-phenyl)-diethylenetriamine of theformula Calculated: N 14.88% CI 37.6% Found: 14.1% 36.5%

From l,2,4,5-tetrachloro-benzene and technical-gradedi(propylene-l,2)-triamine, the compound N'-(2,4,5-trichloro-phenyl)-di(propylene-l ,2')-triamine of the formulaCalculated: N l3.5% Cl 34.l8% Found: l3.8% 34.5%

From l,2,4,5-tetrachloro-benzene and technical-gradetriethylenetetramine, the compoundN'-(2,4,5-trichlorophenyl)-triethylenetetramine of the formula From1,2,4,5-tetrachloro-benzene and technical-gradetri(propylene-l,2)-tetrarnine, the compound N-(2,4,5trichloro-phenyl)-tri( propylene-l',2')-tetramine of the formula hp.163? C./0.03 mm. Hg;

Calculated: N l5.27% Cl 28.95% Found: 151% 29.3%

EXAMPLE 6 l,2,4,5-tetrachloro-benzene is left at boiling temperature(about ll0-l 20 C.) for 40 hours with approximately 10 mols ofethylenediamine in similar manner to the procedure of Example 4. Theworking up gives N-(2,4,5-trichloro-phenyl)- ethylenediamine of theformula hydrochloride (27,) (1 mol) and 120 g. urea (2 mols) are kept atC. for 6 hours in 2 liters of water, with vigorous stirring. After aboutan hour, two phases are formed. The organic phase crystallizes afterstanding for a time at room temperature at the end of the 6-hour period.The crystalline product is separated, washed well with water and, afterdrying, recrystallized from ethylene chloride. Yield: 330 g. ofN-pentachlorophenyl-N'-(amino-carbonyl)-hexamethylenediamine, i.e.,N-[w-(pentachloro-phenyl-amino)-hexyl]-urea, of the formula To asolution of 91 g. N-(pentachlorophenyl)-hexamethylenediamine (5 (0.25mol) in 350 ml. methanol there are added 25 g. succinic anhydride (0.25mol), and the mixture is kept at 50 C. for 1 hour to produceN-[w-(pentachlorophenyl-amino)-hexyll-succinic acid semi-amide 2)- Forsalt formation, 13.5 g. sodium methylate are introduced into thereaction mixture, and the salt is precipitated by addition of L2 litersacetone. Yield: 64 g. of N-[m-(pentachlorophenyl-amino)-hexyl]-succinicacid semiamide sodium salt of the formula C1-- NH-CcHn-NH-O O-C Hz-OH -C0-O-Na I I C1 C1 (122) Calculated: N 5.76% Na 4.73% Found: 5.85% 5.0%

1,,, EXAMPLE 9 159 g. tetrachloro-m-xylene (0.65 mol) and. 850 g.N-(flamino-ethyl)3piperazine (6.6 mols) are heated to 200 C. for

24 hours. The bulk of the excess N-(B-amino-ethyD- I CH Cl H Cl (222) ofboiling point 164' C./0.09 mm. Hg;

C1 3l.60% N [2.48% 3l.6% l2.5%

EXAMPLE By reaction of tetrachloro-m-xylene with hexamethylenediamine ina similar manner to that of Example 9, there is obtainedN-(2,4,6-trichloro-3,5-dimethyl-phenyl)- hexamethylenediamine of theformula Calculated:

Found:

CH Cl Cl NH(CH2) r-NH;

| a CH; Cl (23 of boiling point l50-l52 C./0.08 mm. Hg;

Calculated: CI 32.9% Found: 32.6%

N-( pentaclilorophenyl )-ethylenediamine (2,)N-(pentachlorophenyl)-tetramethylenediamine (4,) N-(pentachlorophenyl-hexamethylenediaminc (5,) N-(pentachlorobenzyl)-hexamethylenediamine (7,) N-[w-( vrrhull,)-hexyl]-fu| (8,) N-pentachlorophenyl-N'-(chloroacetyl)-hexamethylcnediamine (l0,) N'-(pentachlorophenyl )-diethylenetriamine(l3,) 2-[m-(pentachlorophenyl-amino)-hexylamino]- imidazoline-lmethosulfate (l6 N-(pentachlorophenyl)-hexamcthylenediamine acetate andN-(pentachloro-phenyl)-hexamethylenediamine hydrochloride (27,)

are prepared in an analogous manner.

It will be realized by the artisan that all of the foregoing compounds,including the corresponding water soluble salts, contemplated by thepresent invention possess the desired strong algicidal and slimebactericidal properties, with regard to a broad spectrum of activity, aswell as a comparatively low toxicity toward warm-blooded creatures,enabling such compounds to be used with correspondingly favorablecompatibility with warmblooded creatures for more effective controland/or elimination of algae and slime bacteria by application of suchcompounds to such algae and/or slime bacteria and/or their habitat.

lt will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.-

What is claimed is:

1. Method of killing algae and slime bacteria, which comprises applyingto at least one of (a) such algae, (b) such slime bacteria and (c) thecorresponding habitat, a toxic amount of a compound selected from thegroup consisting of an N- chlorophenyl-alkylene polyamine of the formulain which X is selected from the group consisting of hydrogen, chloro andlower alkyl, and n is a whole number from 2-5, at least two of the Xsubstituents being chloro; and the corresponding water-soluble salt ofsaid polyamine.

2. Method according to claim 1 wherein such compound isN-[m(pentachlorophenyl)l-diethylene triamine.

3. Method according to claim 1 wherein such compound isN-(2,4,6-trichloro-3,S-dimethyl-phenyD-hexamethylenediamine.

4. Method according to claim 1 wherein such compoundisN-(pentachlorophenyl)-hexamethylenediamine acetate.

5. Method according to claim 1 wherein such compound is used in the formof a mixture with an inert dispersible carrier vehicle, said compoundbeing present in a toxic amount and constituting substantially betweenabout 0.000l2.5 percent by weight of the mixture.

6. Method according to claim 1 wherein m is a whole number from l3, A isC alkylene, R is hydrogen, R is selected from the group consisting ofhydrogen, CHO, CONE C alkanoyl, chloro- C alkanoyl, carboxyl-C alkanoyl,formamidino, and C alkyl substituted formamidino, Zii s umtal salpfihsfema e a in which X is selected from the group consisting ofhydrogen, chloro and C alkyl, and n is a whole number from 2-5, at leasttwo of the X substituents being chloro, and the correspondingwater-soluble salts are selected form the group consisting of hydrogenhalide, hydrogen sulfate, lower alkyl sulfate, lower alkanoate, benzoateand salicylate ammonium salts.

7. Method according to claim 1 wherein m is a whole number from l-3, thegroup -(NH-A),,, contains up to three N-atoms and up to six carbonatoms, R is hydrogen, R is hydrogen, and Z is a phenyl radical of thefonnula in which X is selected from the group consisting of hydrogen,chloro and C alkyl, and n is a whole number, at least two of the Xsubstituents being chloro, and the corresponding watersoluble salts areselected from the group consisting of hydrogen halide, hydrogen sulfate.lower alkyl sulfate, lower alkanoate, benzoate and salicylate ammoniumsalts.

8. Method according to claim 1 wherein m is 1-3 the group (NHA),,.contains 1-3 N-atoms and 2-6 carbon atoms, R is hydrogen, R is hydrogen,and Z is selected from the group consisting of dichlorophenyl andtrichlorophenyl.

9. Method according to claim 1 wherein such compound is selected fromthe group consisting of N-(pentachlorophenyl)-hexamethylenediamine,

CERTIFICATE OF CORRECTION Paeent No. 3,645,715 I naked Februari 29J 1972Inventofl). Werner Daum, et 9.1;

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

el. 1 line 47 Delete "5" Col. 3' line 30 At line 57 ins ertz v v -C-(ESN -2, S-dichlbtq-phenyl'kdi(propylereeelu2'j-triemine 40-;

C01" 6,- lines 59/61 should read:

tetramine I C I 20 (20 N-[E (2,4,5tr1eh1oro-phenyl-am1hcj v I ethyl]-PiPeraz1ne I t I 1 sighed and sealed this 27th day. or June 1972.

L. (SEAL) Attest:

EDWARD M.FLETCHER,JR. 4 ROBERT GOTTSCHAIK Attesting Officer Commissioner011 Patents

2. Method according to claim 1 wherein such compound is N-( omega(pentachlorophenyl))-diethylene triamine.
 3. Method according to claim 1wherein such compound is N-(2,4,6-trichloro-3,5-dimethyl-phenyl)-hexamethylenediamine.
 4. Methodaccording to claim 1 wherein such compound isN-(pentachlorophenyl)-hexamethylenediamine acetate.
 5. Method accordingto claim 1 wherein such compound is used in the form of a mixture withan inert dispersible carrier vehicle, said compound being present in atoxic amount and constituting substantially between about 0.0001-2.5percent by weight of the mixture.
 6. Method according to claim 1 whereinm is a whole number from 1-3, A is C2-6 alkylene, R1 is hydrogen, R2 isselected from the group consisting of hydrogen, -CHO, -CONH2, C2-4alkanoyl, chloro- C2-4 alkanoyl, carboxyl-C2-4 alkanoyl, formamidino,and C1-4 alkyl substituted formamidino, Z is a phenyl radical of theformula in which X is selected from the group consisting of hydrogen,chloro and C1-4 alkyl, and n is a whole number from 2-5, at least two ofthe X substituents being chloro, and the corresponding water-solublesalts are selected form the group consisting of hydrogen halide,hydrogen sulfate, lower alkyl sulfate, lower alkanoate, benzoate andsalicylate ammonium salts.
 7. Method according to claim 1 wherein m is awhole number from 1-3, the group -(NH-A)m contains up to three N-atomsand up to six carbon atoms, R1 is hydrogen, R2 is hydrogen, and Z is aphenyl radical of the formula in which X is selected from the groupconsisting of hydrogen, chloro and C1-4 alkyl, and n is a whole number,at least two of the X substituents being chloro, and the correspondingwater-soluble salts are selected from the group consisting of hydrogenhalide, hydrogen sulfate, lower alkyl sulfate, lower alkanoate, benzoateand salicylate ammonium salts.
 8. Method according to claim 1 wherein mis 1-3 the group -(NH-A)m contains 1-3 N-atoms and 2-6 carbon atoms, R1is hydrogen, R2 is hydrogen, and Z is selected from the group consistingof dichlorophenyl and trichlorophenyl.
 9. Method according to claim 1wherein such compound is selected from the group consisting ofN-(pentachlorophenyl)-hexamethylenediamine, N-( omega(pentachlorophenyl))-diethylene-triamine,N-(2,4,6-trichloro-3,5-dimethyl-phenyl)-hexamethylene-diamine, andN-(pentachlorophenyl)-hexamethylenediamine acetate.
 10. Method accordingto claim 1 wherein such compound is applied to an algae habitat. 11.Method according to claim 1 wherein such compound is applied to a slimebacteria habitat.